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CHEMISTRY (Theory)
Time allowed : 3 hours
Maximum Marks : 70
General Instructions:
(i)
Write a feature which will distinguish a metallic solid from an ionic solid.
2.
3.
What is an emulsion?
4.
5.
6.
7.
8.
174
9.
10.
11.
12.
13.
14.
15.
16.
Non-ideal solutions exhibit either positive or negative deviations from Raoults law.
What are these deviations and why are they caused? Explain with one example for
each type.
The rate constant for a reaction of zero order in A is 0.0030 mol L 1 s 1. How long
will it take for the initial concentration of A to fall from 0.10 M to 0.075 M ?
Draw the structures of white phosphorus and red phosphorus. Which one of these
two types of phosphorus is more reactive and why?
(ii)
[Co(NH3)4 (H2O)Cl]Cl2
(ii)
Kolbes reaction,
(ii)
Williamson synthesis.
(ii)
17.
Invert sugar
(ii)
Polypeptides
OR
18.
19.
20.
21.
22.
Name the products of hydrolysis of sucrose. Why is sucrose not a reducing sugar?
What are essential and non-essential amino acids in human food? Give one example
of each type.
The well known mineral fluorite is chemically calcium fluoride. It is known that in
one unit cell of this mineral there are 4 Ca2+ ions and 8 F ions and that Ca2+ ions are
arranged in a fcc lattice. The F ions fill all the tetrahedral holes in the face centred
8
cubic lattice of Ca2+ ions. The edge of the unit cell is 5.46x10 cm in length. The
3
density of the solid is 3.18 g cm . Use this information to calculate Avogadros
1
number (Molar mass of CaF2 = 78.08 g mol )
What is the difference between multi molecular and macromolecular colloids? Give
one example of each type. How are associated colloids different from these two
types of col1oids ?
(ii)
(iii)
OR
Describe the role of
(i)
(ii)
(iii)
24.
25.
The atomic radii of the metals of the third (5d) series of transition elements are
virtually the same as those of the corresponding members of the second (4d)
series.
(ii)
The E value for the Mn3+/Mn2+ couple is much more positive than that for
Cr3+/Cr2+ couple or Fe3+/Fe2+ couple.
(iii)
(i)
(ii)
Which compound in the following couples will react faster in SN2 displacement
and why?
(a)
1-Bromopentane or 2-bromopentane
(b)
1-Bromo-2-methylbutane or 2-bromo-2-methylbutane.
(ii)
(iii)
177
26.
27.
28.
addition polymers,
(ii)
condensation polymers,
(iii)
copolymers.
What are analgesic medicines? How are they c1assifiedand when are they
commonly recommended for use?
(a)
(b)
Calculate
OR
29.
(a)
Write the anode and cathode reactions and the overall reaction occurring in a
lead storage battery.
(b)
A copper-silver cell is set up. The copper ion concentration is 0.10 M. The
concentration of silver ion is not known. The cell potential when measured
was 0.422 V. Determine the concentration of silver ions in the cell. (Given
o
o
E Ag+/Ag = + 0.80 V, E cu2+/cu = + 0.34 V)
(a)
NaOH(aq) + Cl2(g)
(Hot and cone.)
(ii)
XeF6(s) + H2O(l)
178
(b)
The value of electron gain enthalpy with negative sign for sulphur is
higher than that for oxygen.
(ii)
(iii)
ClF3 molecule has a T-shaped structure and not a trigonal planar one.
OR
(a)
(b)
30.
P4 + SO2Cl2
(ii)
XeF4 + H2O
(ii)
(iii)
(a)
(b)
(a)
(ii)
(b)
(ii)
Ethanal to but-2-enal
(iii)
Propanone to propene
What type of interactions hold the molecules together in a polar molecular solid?
2.
3.
4.
H3C
CH3
=
H
H
CH3
5.
Br
6.
7.
8.
9.
Define the terms, osmosis and osmotic pressure. What is the advantage of using
osmotic pressure as compared to other colligative properties for the determination
of molar masses of solutes in solutions?
180
10.
11.
Express the relation among the cell constant, the resistance of the solution in the cell
and the conductivity of the solution. How is the conductivity of a solution related to
its molar conductivity?
OR
Two half-reactions of an electrochemical cell are given below:
MnO 4 (aq) + 8 H (aq) + 5 e Mn (aq) + 4 H2O (l), E = + 1.51 V
2+
12.
13.
14.
4+
Construct the redox reaction equation from the two half-reactions and calculate the
cell potential from the standard potentials and predict if the reaction is reactant or
product favoured.
(i)
Tyndall effect
(ii)
Shape-selective catalysis
(i)
I2 + HNO3
(cone.)
(ii)
HgCl2 + PH 3
181
15.
16.
17.
18.
19.
20.
21.
H4P 2 O 5
(ii)
XeF4
Give the chemical tests to distinguish between the following pairs of compounds:
(i)
(ii)
CH3CH2Cl
(ii)
C6H5NH2
PVC
(ii)
Teflon
The density of copper metal is 8.95 g cm 3. If the radius of copper atom be 127.8
pm, is the copper unit cell simple cubic, body-centred cubic or face-centred cubic?
(Given: atomic mass of Cu = 63.54 g mol 1 and NA = 6.02 x 1023 mol1)
What mass of NaCl (molar mass = 58.5 g mol 1) must be dissolved in 65 g of water
o
to lower the freezing point by 7.50 C ? The freezing point depression constant, Kf,
for water is 1.86 K kg mol 1. Assume vant Hoff factor for NaCl is 1.87.
(i)
(ii)
(iii)
OR
Describe the principle involved in each of the following processes of metallurgy :
22.
23.
24.
25.
26.
(i)
(ii)
(iii)
(ii)
(iii)
How would you differentiate between SN1 and SN2 mechanisms of substitution
reactions? Give one example of each.
(i)
Phenol to benzoquinone
(ii)
Propanone to 2-methylpropan-2-ol
(iii)
Propene to propan-2-ol
(i)
(ii)
(iii)
The electron gain enthalpy with negative sign for fluorine is less than that for
chlorine, still fluorine is a stronger oxidising agent than chlorine.
Amino acids may be acidic, alkaline or neutral. How does this happen? What are
essential and non-essential amino acids? Name one of each type.
183
27.
28.
Food preservatives
(ii)
Enzymes
(iii)
Detergents
(a)
(b)
(i)
Rate of a reaction
(ii)
P4 (g) + 6 H2 (g)
(ii)
(a)
(b)
Order of a reaction
(ii)
Molecularity of a reaction
The rate of a reaction increases four times when the temperature changes
from 300 K to 320 K. Calculate the energy of activation of the reaction,
assuming that it does not change with temperature. (R = 8.314 J K1 mol 1)
184
29.
(a)
(b)
(i)
(ii)
Cu (aq) + I (aq)
2+
(i)
The oxidising power of oxoanions are in the order VO 2 < Cr2O 7 <
MnO 4 .
(ii)
(iii)
(a)
(b)
30.
(a)
(b)
(i)
(ii)
La3+ (Z = 57) and Lu3+ (Z = 71) do not show any colour in solutions.
(ii)
(iii)
Illustrate the following name reactions giving a chemical equation in each case:
(i)
Clemmensen reaction
(ii)
Cannizzaros reaction
Cyclohexanol to cyclohexan-l-one
185
(ii)
(iii)
OR
(a)
(b)
(ii)
(ii)
(iii)
186
The Marking Scheme provides general guidelines to reduce subjectivity in the marking.
The answers given in the Marking Scheme are suggested answers. The content is thus
indicative. If a student has given any other answer which is different from the one given
in the Marking Scheme, but conveys the same meaning, such answers should be given
full weightage.
2.
The Marking Scheme carries only suggested value point for the answers. These are
only guidelines and do not constitute the complete answers. The students can have
their own expression and if the expression is correct the marks, will be awarded
accordingly.
3.
Some of the questions may relate to higher order thinking ability. These questions have
been indicated by the mark* and the students understanding/analytical ability may be
judged. These questions are to be evaluated carefully.
4.
5.
6.
If a question has parts, please award marks in the right hand side for each part. Marks
awarded for different parts of the question should then be totalled up and written in the
left hand margin and circled.
7.
If a question does not have any parts, marks be awarded in the left-hand margin.
8.
If a candidate has attempted an extra question, marks obtained in the question attempted
first should be retained and the other answer should be scored out.
9.
10.
A full scale of marks 0-70 has to be used. Please do not hesitate to award full marks
if the answer deserves it.
187
Mode of conduction, through electrons in solid metal and through ions in molten
state or in solution in ionic solid / Metals are malleable and ductile whereas ionic
solids are hard and brittle.
The sum of powers of the concentration of the reactants in the rate law expression
is called the order of that chemical reaction.
Ph CO CH2-CH3
But-3-en-1-amine
When the vapour pressure of a non-ideal solution is either higher or lower than that
predicted by Raoults law, the solution exhibits deviations.
Positive deviation eg: mixture of ethanol and acetone, carbon-disulphide and ace-
10
Negative deviation eg: Chloroform and acetone, nitric acid and water (any one)
Rate = k[A][B]2
(i)
Rate = k[A][3B]2
188
= 9k[A][B]2
= 9 times the initial Rate1 i.e. rate is increased 9 times
(ii)
Rate = k[2A][2B]2
= 8k[A][B]2
= 8 times the initial Rate i.e. rate is increased 8 times
11
[R]t = - kt + [R]0
1
P
P
White Phosphorus
PP
PP
P
P
P
P
Rod Phosphorus
White phosphorus is more reactive due to its discrete tetrahedral structure and
angular strain
13
14
15
(i)
(ii)
(i)
Tetraammineaquachloridocobalt(III) chloride
(ii)
Dichloridobis(ethane-1,2-diamine)chromium(III) chloride
(i)
Kolbes Reaction
189
1+1
1+1
OH
ONa
OH
COOH
(i) CO2
NaOH
(ii) H+
2-Hydroxybenzolc acid
(Salicylio acid)
(ii)
Williamson Synthesis
RONa + RBr R O R + NaBr
(i)
CH2 CI
CH2 OH
ag.NaOH
(ii)
CH3MgBr
O
||
CH3C CH3
OMgBr
|
CH3 C CH3
|
CH3
H 2O
OH
|
CH3 C CH3
|
CH3
i)
ii)
OR
Products of hydrolysis of sucrose are : Glucose and Fructose
190
18
Amino acids which must be supplied in our diet are called Essential Amino Acids
eg. Leucine, Isoleucine, Valine (any one)
Amino acids which can be made by our bodies and not required in our diet are
called non-essential Amino Acids eg. Glycine, Alanine (any one)
19
d = z3 x M
a x NA
For fcc lattice z = 4
1
4 x 78.08 g mol -1
-3
3.18 g cm =
( 5.46 x 10 -8 cm )3 x NA
4 x 78.08 g mol -1
NA =
( 5.46 x 10 -8 cm )3 x 3.18 g cm-3
NA = 6.033 x 1023 mol -1
20
1
1.25g x 1000
M
99kg
M 152 g mol -1
1
1
Multimolecular colloids
Macromolecular colloids
of colloidal dimensions
Example :Starch
Associated colloids are those which at low concentration behave as normal electolytes & at high concentration act as colloids.
191
22
i)
Pig iron is converted into steel by adding carbon and some other elements.
ii)
Or ZnO + C
iii)
Zn + CO
Impure titanium is heated with Iodine to form volatile complex TiI4 which
on further heating to higher temperature decomposes to give pure titanium.
1x3 = 3
or
4Au(s) + 8CN-(aq) + 2H2O + O2(g)
(ii)
4[Au(CN)2]- + 4OH-
SiO2 is added in copper matte to convert the remaining FeS, FeO to slag.
or
FeSiO3(slag)
FeO + SiO2
(iii)
23
ZrI4
Zr(pure) + 2I2
(i)
(ii)
Due to stable half filled 3d5 configuration of Mn2+ / high 3rd ionisation enthalpy
of Mn.
24
(iii)
(i)
(ii)
192
1x3 = 3
25
26
27
(i)
(ii)
(iii)
(i)
(ii)
(iii)
1x3 = 3
1x3 = 3
Non Narcotic Drugs are effective in relieving skeletal pain / preventing heart attack /
viral inflammation, etc.
Narcotic Drugs are recommended for the relief in postoperative pains / Cardiac
pain / terminal cancer.
28
(i)
The law states that limiting molar conductivity of an electrolyte can be represented as the sum of the individual contributions of the Anion and Cation
of the electrolyte.
m (HAc) = H+ + Ac-
o
(ii)
CH3COOH =
=
=
CH3COONa
( 91
2
o
HCI
426
391 S cm mol
-1
OR
193
NaCI
1
1
1
(i)
Net reaction:(ii)
Nernst equation
o
2
Ecell =
0.46V
[ Ag+]2
(a)
(i)
6NaOH + 3Cl2
(ii)
XeF6 + H2O
XeOF4 + 2HF
or
XeF6 + 2H2O
XeO2F2 + 4HF
or
XeF6 + 3H2O
XeO3 + 6HF
194
(b)
(i)
(ii)
Becuase bond energy of F2 is lower than Cl2 and N-F bond is smaller
& stronger than N-Cl bond.
(iii)
1x3 = 3
OR
(a)
(i)
P4 + 10SO2Cl2
(ii)
6XeF4 + 12H2O
4PCl5 + 10SO2
2XeO3 + 4Xe + 24HF + 3O2
1+1
(i)
Becuase down the group, +3 oxidation state becomes more & more
stable due to higher energy involved to unpair the s electrons / due to
inert pair effect.
30
(ii)
(iii)
1x3 = 3
(a)
195
(b)
CH 3CH 2CH 2COOCH 2CH 2CH 2CH 3
CH3CH2CH2CH2 OH
CH3CH2CH2COOH
CH3CH2CH2 CH2OH
CH3CH2CH=CH2
1x3 = 3
OR
(a)
COCI
CHO
H2,pd-BaSo4
PCls
OH
|
(ii) 2CH3 CHO
(iii) CH3 C CH3
||
O
CH3 CH = CH CHO
CH3 CH CH3
|
OH
CH3 CH = CH2
1x3 = 3
4-bromo-3-methyl pent-2-ene
C6H5-CH2-CH(OH)-CH3
Ammoniacal solution of silver nitrate is called Tollens reagent. It is used as an oxidizing reagent / test for CHO group.
Carbohydrates which reduce Tollens reagent or Fehling solution are called reducing
sugars which have free aldehydic group.
1
The flow of solvent from solution of low concentration to higher concentration through
semipermeable membrane is called osmosis.
The hydrostatic pressure that has to be applied on the solution to prevent the entry
of the solvent into the solution through the semipermeable membrane is called the
Osmotic Pressure.
Advantage: Unlike other colligative properties, osmotic pressure is used to determine the Molar mass of macromolecules/polymers like protein / or any other advantage
k = 1/R (l/A)
10
11
Ag+ / Ag < Cu2+ / Cu < Fe2+ / Fe < Cr3+ / Cr < Mg2+ / Mg < K+ / K
OR
Redox Reaction
2MnO4- + 5Sn2+ + 16H+
Ecell = EC-EA
= (+1.51 0.15)V = +1.36V
Tyndall Effect:- The scattering of light by the colloidal particles present in a colloidal sol is called Tyndall effect
1+1
Shape Selective Catalysis:- The catalytic reaction that depends upon the pore
structure of the catalyst and the size of the reactant and product molecules is called
shape-selective catalysis.
13
(i)
I2 + 10HNO3
(ii)
3HgCl2 + PH3
Hg3P2 + 6HCl
1+1
(i)
HO
H
P
O
P
OH
H
1+1
198
16
18
19
(i)
A = CH3 CH2 CN
(ii)
A = C6 H5 N2 Cl
(i)
CH2=CH-Cl
(ii)
CF2=CF 2
d=
z x M__
N=N
+
NH2
1+1
a3 x NA
Assuming fcc lattice for copper
a = 2v2 r
a3 = (2v2 r)3
4 x 63.54 g mol-1
4.723 x 10-23 cm3 x 6.02 x 1023 mol-1
= 8.94 g cm-3
Note: If any other lattice is assumed, comparing the density or z-value with
the given one, may be accepted as the right procedure.
199
20
Tf = 7.50C
Tf = iKf m
1
w
-1
58.5g mol
21
(i)
1000
65 kg
w = 8.2g
or
4Ag(s) + 8CN(aq) + 2H2O + O2(g)
(ii)
4[Ag(CN)2] + 4OH
or
Ti(impure) + 2I2
TiI4
(iii)
TiI4
Ti(pure) + 2I2
OR
(i)
Froth Floatation method:- The mineral particles become wet by oils while
the gangue particles by water.
(ii)
Electrolytic refining: Crude metal is made as anode and pure metal as cathode. When current is passed through electrolyte of same metal ions then pure
metal gets deposited at cathode and impurities settle at bottom of anode.
(iii)
Zone Refining:- The impurities are more soluble in the melt than in the solid
state of the metal.
200
1x3 = 3
22
23
(i)
1x3 = 3
(ii)
(iii)
Because crystal field splitting energy is more than compensated for the third
ionisation enthalpy.
In SN1 it occurs in two steps and the reaction is of first order whereas in SN2 it
occurs in one step and the reaction is of second order.
or
OH + H
H
C1
HO
C1
H
HO
H + Cl
H
SN1 example:
CH3
(CH3)3 CBr
CH3
H3C
+ OH
H3C
24
(i)
OH
+ Br
CH3
(CH3)3COH
CH3
201
CH3
|
25
(ii)
CH3 C CH3
||
O
CH3 C CH3
|
OH
(iii)
CH2 = CH CH3
CH3 CH CH3
|
OH
(i)
Because (a) bond dissociation enthalpy of F2 is lower than that of Cl2 and
(b) small size F atom forms stronger bond with N.
26
(ii)
(iii)
1x3 = 3
1x3 = 3
Acidic amino acids contain more number of carboxyl groups than amino groups.
Basic amino acids contain more number of amino groups than carboxyl groups.
Neutral amino acids contain equal number of amino acids and carboxyl groups.
(i)
(ii)
Food preservatives: are the compounds which prevent spoilage of food due
to microbial growth. eg: sodium benzoate, vinegar (any one example)
Enzymes are the biological catalysts which increase the rate of metabolism.
eg: Invertase, Zymase, (or any other one example)
202
(iii)
28
(a)
Detergents are sodium salts of long chain alkyl sulphonates or benzene sulphonates. eg: Sodium Lauryl sulphate.
(i)
Rate of a reaction- Rate of Change of concentration of reactant or product with time is called rate of reaction
(ii)
1+1
or
The energy required by the reactant molecules for the formation of intermediate
activated complex
(b) (i) t 1/2 = 0.693
k
k=
0.693
37.9
s-1
k = 0.0183s 1
t=
2.303
log [ A0 ]
-1
0.183s
[A]
t=
2.303
0.183s-1
log 1 .
1/4
t = 75.84s
(ii)
k=
2.303
60s
log [ A0 ]
[A]
log [ A0 ]
[A]
= k x 60
2.303
= 0.0183 x 60
2.303
203
log [ A0 ]
[A]
= 0.4762
2.999
Therefore, [ A ] =
[A0]
0.33
OR
(a)
(b)
(i)
The sum of powers of the concentration of the reactants in the rate law
expression is called the order of that chemical reaction.
(ii)
log k2
k1
log 4 =
0.6020 =
Ea
2.303 R
T2- T1
T1 T2
Ea
2.303 x 8.314 JK-1 mol-1
Ea
320- 300
300 x 320
K-1
96 x 103
= 55336.7 J mol-1
= 55.33 kJ mol-1
29
(a)
(b)
20 K-1
1+1
(i)
2Cr3+ + 7H2O + 3S
(ii)
2Cu2+ + 4I
(i)
Cu2I2 + I2
204
1+1
(ii)
(iii)
1x3 = 3
OR
(b)
(i)
(ii)
(i)
1+1
(i)
30
(a)
(i)
Cu2+ + Cu
Clemmensen reduction
Zn - Hg
C=O
CH2 + H2O
HC1
(a)
(ii)
Cannizzaro reaction:
H
H
C=O +
C=O
KOH (conc.)
formaldehyde
H
|
H C OH
|
H
Methanol
O
+
H C
OK
sodium formate
205
1x3 = 3
(b)
(i)
OH
(i)
C2H5
COOH
(iii)
Br
MgBr
COOMgBr
COOH
1x3 = 3
(i)
Hell-Volhard-Zelinsky reaction
R-CH2COOH
R CH COOH
|
X
X = Cl, Br
(ii)
Wolf-kishner reduction
C=O
C = NNH2
CH2 + N2
(wolff-Kishner rduction)
(b)
(i)
C2H5 CN
CH3 CH2 OH
CH3COOH
(ii)
(i)
CH3
206
1x3 = 3